CN100484667C - Method of preparing pyrite powder as electrode material of high-energy lithium-iron battery - Google Patents
Method of preparing pyrite powder as electrode material of high-energy lithium-iron battery Download PDFInfo
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- CN100484667C CN100484667C CNB2007100730095A CN200710073009A CN100484667C CN 100484667 C CN100484667 C CN 100484667C CN B2007100730095 A CNB2007100730095 A CN B2007100730095A CN 200710073009 A CN200710073009 A CN 200710073009A CN 100484667 C CN100484667 C CN 100484667C
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Abstract
Iron buff powder for high energy lithium metal battery electrodes starts with baking the metal powder in 100deg.C- 400deg.C temperature for 2-5 hours in sealed vacuum container, then in the inert gas further heating 10-20 hours in 500deg.C-600deg.C temperature, cooling to normal temperature and ball grinding for 3-5 hours, sorting out those above 300 Deg C and sealing it. It has higher purity ratio and thermostatic feature, with low inner resistance, quick reaction speed, high big current discharge platform, without concave peak voltage.
Description
Technical field
The present invention relates to a kind of positive active material processing method of high energy lithium Fe battery, specifically a kind of method for preparing pyrite powder as electrode material of high-energy lithium-iron battery.
Background technology
One time the high energy lithium Fe battery has obtained huge development in recent years, the particularly development of the electronic apparatus of digital camera and so on, bright prospects are provided, have simultaneously also proposed more and more higher requirement: specific energy is big, security good, environmental protection, self discharge is little and littler lighter.
The improvement of a high energy lithium Fe battery performance depends primarily on the improvement of the pyrite dust (Main Ingredients and Appearance is a ferrous disulfide) in the electrode anode.Current battery producer, employed pyrite dust in the electrode anode of making lithium Fe battery, generally be without any processing, will be from the pyrite dust directly buied on the market as one of electrode anode material of battery, with the made battery of undressed former pyrite dust, have recessed peak voltage, discharge platform is low and self discharge is big problem.
Summary of the invention
The objective of the invention is: a kind of method for preparing pyrite powder as electrode material of high-energy lithium-iron battery is provided, and this method both can improve pyritous purity, can also improve the high thermal stability of ferrous disulfide.
Basic ideas of the present invention are: to existing former pyrite dust from buying on the market, carry out the vacuum and low temperature baking earlier, carry out high-temperature process again under the protection of inert gas, last ball milling sieves and obtains required finished product.
Its tool step is as follows:
A kind of method for preparing pyrite powder as electrode material of high-energy lithium-iron battery comprises the steps:
(1), in airtight container, vacuum, with pyrite dust with 100 ℃～400 ℃ temperature baking 2～5 hours;
(2), will in inert gas atmosphere, continue again through the pyrite powder after the above-mentioned processing with 500 ℃～600 ℃ temperature bakings 10～20 hours;
(3), be cooled to room temperature, ball milling is 3～5 hours in ball mill;
(4), the above vibratory sieve of 300 orders sieves, pack.
The temperature preferred values in described second step is 550 ℃ ± 15 ℃; Stoving time is 15 hours ± 3 hours.
Described vacuum is 0.1～-0.1Mpa.
Ball of the different Stainless Steels of φ 5～φ 25 is housed in described ball mill.
Described inert gas is an argon gas.
The present invention has following advantage: with the made pyrite dust of the inventive method, its pyrite dust has the purity height, the advantage that heat endurance is high, use it for the active material of lithium Fe battery positive pole, it is low that its lithium Fe battery of producing has internal resistance, and reaction speed is fast, heavy-current discharge platform height, substantially do not have recessed peak voltage, absorbency is good, the advantage that self discharge is little.
The specific embodiment
Directly use undressed pyrite dust, its Main Ingredients and Appearance is the ferrous disulfide (FeS that contains about 94%
2), all the other compositions are As and Fe
-, Co
2-, Ni
2+, S
-The anode material that is made into lithium Fe battery uses, and why the lithium Fe battery made from this anode material has recessed peak voltage and the low problem of discharge platform; Mainly be the problem that there is the following aspects in undressed pyrite dust, the one, the ferrous disulfide content of pyrite dust is low; The 2nd, undressed pyrite dust poor heat stability; The 3rd, the pyrite dust bulk density is low; The 4th, the liquid absorption of pyrite dust is low.This method first step under vacuum state, is toasted pyrite dust 2～5 hours with 100 ℃～400 ℃; It mainly is the content that helps improving the ferrous disulfide of pyrite dust, impurity S
+Can be oxidized, produce SO
2Vapor away. and then improved the relative amount of ferrous disulfide in the pyrite dust:
Through test, by the pyrite dust after the first step processing, the content of its ferrous disulfide improves a lot, and sees Table 1.
Table 1 is through the content of FeS2 in different temperatures and the time processing pyrite
As can be seen from the above table, with the undressed pyrite dust that contains more than or equal to 74% ferrous disulfide, be 0.1 to the atmosphere of negative 0.1MPA in vacuum, under constant situation of time, along with the increase of temperature, the content of its ferrous disulfide is to improve gradually; Under temperature-resistant situation, along with the prolongation of time, the content of its ferrous disulfide also is to increase to some extent, and the pyrite dust after this method first step is handled is described, compare with ferrous disulfide (74%) content in the undressed pyrite dust, can improve about 22 percentage points.
In addition, with the pyrite dust after the first step processing of this method, its bulk density and liquid absorption all increase (referring to table 2 and table 3) to some extent.
Table 2 is through the influence of bulk density in the pyrite of treatment of different temperature
| Treatment temperature (℃) | (74.5%) is untreated | 100 | 150 | 200 | 300 | 350 | 400 |
| FeS 2(g/cm3) | 1.287 | 1.295 | 1.327 | 1.328 | 1.357 | 1.409 | 1.421 |
| Treatment temperature (℃) | (85.2%) is untreated | 100 | 150 | 200 | 300 | 350 | 400 |
| FeS 2(g/cm3) | 1.394 | 1.395 | 1.396 | 1.396 | 1.412 | 1.421 | 1.428 |
| Treatment temperature (℃) | (94.7%) is untreated | 100 | 150 | 200 | 300 | 350 | 400 |
| FeS 2(g/cm3) | 1.405 | 1.410 | 1.413 | 1.420 | 1.424 | 1.427 | 1.430 |
The pyrite dust of table 3 process treatment of different temperature is to the influence of liquid absorption
| Temperature (℃) | Liquid absorption (100 gram FeS2) | Pick up (%) |
| (74.5%) is untreated | 19.7 | 19.7 |
| 100 | 21.78 | 21.78 |
| 200 | 25.86 | 25.86 |
| 300 | 28.59 | 28.59 |
| 400 | 31.74 | 31.74 |
| (85.2%) is untreated | 19.7 | 19.7 |
| 100 | 21.83 | 21.83 |
| 200 | 25.89 | 25.89 |
| 300 | 28.61 | 28.61 |
| 400 | 31.77 | 31.77 |
| (94.7%) is untreated | 19.7 | 19.7 |
| 100 | 22.18 | 22.18 |
| 200 | 25.91 | 25.91 |
| 300 | 28.68 | 28.68 |
| 400 | 31.78 | 31.78 |
Second step of this method will in inert gas atmosphere, continue with 500 ℃～600 ℃ temperature bakings 10～20 hours through the pyrite dust after the above-mentioned first step is handled again; Can improve pyrite dust knot body structure.Pyrite dust has two kinds of crystal forms, i.e. P type crystal and N type crystal, and pyrite dust is when unprocessed, it mainly is a P type crystal, still, and for improving battery performance, desired is the high as far as possible N type crystal that contains, and second step handled, and helps improving the content of the N type crystal of pyrite dust.Through test, second one step process can improve the content of the N type crystal in the pyrite dust.Referring to table 4.
Table 4 is handled pyritous XRD parameter list through different temperatures and time
From the analysis of XRD (table 4) as can be known, the FWHM value of the face of the pyritous front and back of heat treatment diminishes, and lattice parameter generation obvious variation is described.After the heat treatment, pyritous structure cell is changed toward little aspect, therefore cause battery to change at discharge performance.According to formula 2dsin θ=n λ (d: interplanar distance; θ: the angle of diffraction; N: λ progression; λ: the diffraction light wavelength) with for the formula of isometric system mineral
The mean value of result of calculation be: 200 ℃ are handled 15 hours is 158.87; 550 ℃ are handled 15 hours is 156.98.Being called as the crystal that forms when low temperature is P type crystal; The crystal that forms when high temperature is a N type crystal, and according to the argumentation of HOBrOPORBa etc.: high temperature helps Co, and Ni replaces the iron in the pyrite, As during high temperature, Sb unstability in the pyrite structure, and low temperature helps As, and Sb enters and replaces sulphur in the pyrite.Therefore the N type crystal in the pyrite forms when high temperature, and the result that P type crystal forms when low temperature also is consistent.
X-ray diffraction is a kind of effective method that is used for determining the pyrite crystal structure.So obtain the XRD parameter of table 4, the crystal of pyrite dust changes when low temperature not quite, be P type crystal, after the high-temperature process, 2 θ values increase gradually and are in stable, interplanar distance d reduces gradually, diffraction maximum moves to right gradually, and half peak breadth increases, and causes grain size to reduce, produce the change of crystal like this, be N type crystal.
In addition, with the aforementioned pyrite dust after second step processing of this method, its bulk density and liquid absorption all increase (referring to table 5 and table 6) to some extent.
Table 5 is through the influence of bulk density in the pyrite of treatment of different temperature
| Treatment temperature (℃) | 500 | 600 |
| FeS2(g/cm3) | 1.431 | 1.431 |
The pyrite of table 6 process treatment of different temperature is to the influence of liquid absorption
| Temperature (℃) | Liquid absorption (100 gram FeS2) | Pick up (%) |
| 500 | 31.95 | 31.95 |
| 600 | 31.96 | 31.96 |
Through campaign, our pyrite dust after by the first step and the processing in second step is equipped with the ball mill ball milling 3～5 hours of ball of the different Stainless Steels of φ 5～φ 25 in being used in ball mill, sieve more than 300 orders, and is standby.
Now with the pyrite dust of above-mentioned processing as one of composition of anode material, with untreated pyrite dust as one of composition of anode material, the cell of making compares (table 7), the performance of battery is significantly improved.The preparation method of galvanic anode and component are identical with an existing high energy lithium Fe battery anode preparation method and component, by those of ordinary skill of the same trade is known, so repeated description no longer here.(contain FeS with untreated pyrite dust
285.2%) made AA battery (discharge current is 1000mA), the V1 of described battery, V2, m Ω, C1, C2 are respectively: 0.97; 1.50; 440; 2780; 2193.
Table 7 (contains FeS through the pyrite dust of different temperatures and time processing
297.6%) result's (with AA is example, and discharge current is 1000mA) of trial-production battery
In the table 7: V1: be expressed as crest voltage; V2: be expressed as load voltage, its load is 3.9 Ω; M Ω is expressed as internal resistance; C1 is expressed as the test capacity after 7 days; C2 is expressed as the test capacity after 30 days.
V1, V2, m Ω, C1, the C2 value of the V1 in the table 7, V2, m Ω, C1, C2 and untreated pyrite dust are compared, be not difficult to find out, its lithium Fe battery of producing has and does not have recessed peak voltage (V1 value) substantially, internal resistance low (m Ω value), heavy-current discharge platform height (V2 value), capacity big (C1 value), the advantage of self discharge little (C1 and C2's is poor) has improved the electric property of lithium Fe battery.Above-mentioned battery examples (contains FeS though only enumerated a kind of untreated pyrite dust
285.2%), with a kind of handle after pyrite dust (contain FeS
297.6%) result that compares of made battery, but in the reality, the high more battery of doing of the content of ferrous disulfide in the pyrite dust, its electric property is good more to be the common practise of the industry.So do not enumerate other comparing result here one by one.
Take a broad view of it, we are that described low temperature and second Buwen's degree are 550 ℃ ± 15 ℃ by the first step in temperature; Stoving time is that the processing under 15 hours ± 3 hours the environmental condition can be made preferable pyrite.
Claims (4)
1, a kind of method for preparing pyrite powder as electrode material of high-energy lithium-iron battery, it is characterized in that: this method comprises the steps:
(1), in airtight container, vacuum, with pyrite dust with 100 ℃ of-400 ℃ of temperature baking 2～5 hours;
(2), will be through the pyrite powder after the above-mentioned processing, again in inert gas atmosphere,
Continue with 500 ℃～600 ℃ temperature bakings 10～20 hours;
(3), be cooled to room temperature, ball milling is 3～5 hours in ball mill;
(4), sieve more than 300 orders, pack.
2, the method for preparing pyrite powder as electrode material of high-energy lithium-iron battery according to claim 1 is characterized in that: the temperature preferred values in described second step is 550 ℃ ± 15 ℃; Stoving time is 15 hours ± 3 hours.
3, the method for preparing pyrite powder as electrode material of high-energy lithium-iron battery according to claim 1 and 2 is characterized in that: different stainless ball that φ 5～φ 25 is housed in described ball mill.
4, the method for preparing pyrite powder as electrode material of high-energy lithium-iron battery according to claim 3 is characterized in that: described inert gas is an argon gas.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3160496A (en) * | 1961-03-28 | 1964-12-08 | Montedison Spa | Process for treating ironpyrites |
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|---|---|---|---|---|
| US3160496A (en) * | 1961-03-28 | 1964-12-08 | Montedison Spa | Process for treating ironpyrites |
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Effective date of registration: 20151118 Address after: High tech Zone 277100 Shandong city of Zaozhuang province Thailand five Road Industrial Park, Fuyuan Electronics Group. Patentee after: Shandong Seiko Electronic Technology Co.,Ltd. Address before: 277100, Guangming West Road, Xuecheng District, Zaozhuang District, Shandong, 15 Patentee before: SHANDONG SHENGONGHAITE ELECTRONIC TECHNOLOGY LTD. |
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Address after: 277800 No. x6699, Guangming Road, high tech Zone, Zaozhuang City, Shandong Province (north of the junction of Guangming Road and Huaxin Road) Patentee after: Shandong Jinggong Electronic Technology Co.,Ltd. Address before: 277100 Haite Electronics Group, Fuyuan 5th Road, Thailand Industrial Park, High tech Zone, Shandong Province Patentee before: Shandong Seiko Electronic Technology Co.,Ltd. |
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